Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

MODIS Biophysical States and NEXRAD Precipitation in a Statistical Evaluation of Antecedent Moisture Condition and Streamflow1

Abstract: The potential of remotely sensed time series of biophysical states of landscape to characterize soil moisture condition antecedent to radar estimates of precipitation is assessed in a statistical prediction model of streamflow in a 1,420 km² watershed in south‐central Texas, Moderate Resolution Imaging Spectroradiometer (MODIS) time series biophysical products offer significant opportunities to characterize and quantify hydrologic state variables such as land surface temperature (LST) and vegetation state and status. Together with Next Generation Weather Radar (NEXRAD) precipitation estimates for the period 2002 through 2005, 16 raw and deseasoned time series of LST (day and night), vegetation indices, infrared reflectances, and water stress indices were linearly regressed against observed watershed streamflow on an eight‐day aggregated time period. Time offsets of 0 (synchronous with streamflow event), 8, and 16 days (leading streamflow event) were assessed for each of the 16 parameters to evaluate antecedent effects. The model results indicated a reasonable correlation (r² = 0.67) when precipitation, daytime LST advanced 16 days, and a deseasoned moisture stress index were regressed against log‐transformed streamflow. The estimation model was applied to a validation period from January 2006 through March 2007, a period of 12 months of regional drought and base‐flow conditions followed by three months of above normal rainfall and a flood event. The model resulted in a Nash‐Sutcliffe estimation efficiency (E) of 0.45 for flow series (in log‐space) for the full 15‐month period, ?0.03 for the 2006 drought condition period, and 0.87 for the 2007 wet condition period. The overall model had a relative volume error of ?32%. The contribution of parameter uncertainties to model discrepancy was evaluated.     

Composting clam processing wastes in a laboratory- and pilot-scale in-vessel system

Waste materials from the clam processing industry (offal, shells) have several special characteristics such as a high salinity level, a high nitrogen content, and a low C/N ratio. The traditional disposal of clam waste through landfilling is facing the challenges of limited land available, increasing tipping fees, and strict environmental and regulatory scrutiny. The aim of this work is to investigate the performance of in-vessel composting as an alternative for landfill application of these materials. Experiments were performed in both laboratory-scale (5L) and pilot-scale (120L) reactors, with woodchips as the bulking agent. In the laboratory-scale composting test, the clam waste and woodchips were mixed in ratios from 1:0.5 to 1:3 (w/w, wet weight). The high ratios resulted in a better temperature performance, a higher electrical conductivity, and a higher ash content than the low-ratio composting. The C/N ratio of the composts was in the range of 9:1-18:1. In the pilot-scale composting test, a 1:1 ratio of clam waste to woodchips was used. The temperature profile during the composting process met the US Environmental Protection Agency sanitary requirement. The final cured compost had a C/N ratio of 14.6, with an ash content of 167.0+/-14.1g/kg dry matter. In addition to the major nutrients (carbon, nitrogen, calcium, magnesium, phosphorus, potassium, sulfur, and sodium), the compost also contained trace amounts of zinc, manganese, copper, and boron, indicating that the material can be used as a good resource for plant nutrients.     

Fe-厌氧微生物体系降解2,4,6-三氯酚

采用Fe-厌氧微生物体系降解2,4,6-三氯酚(2,4,6-TCP).在初始pH 7.0、Fe加入量10.0 g/L、以甲酸钠为碳源的条件下,2,4,6-TCP降解效果最好.采用Fe-厌氧微生物体系降解2,4,6-TCP,比单独采用Fe或厌氧微生物体系具有明显的效果,运行60h后2,4,6-TCP开始降解,108h后2,4,6-TCP降解完全.添加2-溴乙烷磺酸盐可抑制产甲烷菌的活性,能有效促进2,4,6-TCP的降解.     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

城市家用天然气安全管理的研究

通过对100家广州市天然气家庭用户使用情况进行调查,主要针对天然气使用、燃气设施保护和安全意识等诸多问题,运用事故致因理论,分析其成因规律,提出从事故发生的根本原因入手,运用"预防为主、善后为辅"的积极、主动的方法,把事故消除在起始或孕育阶段。调查结果显示:造成城市燃气应用系统事故的原因主要包括:用户燃具不正确的选择、燃气设备安装不当、燃气安全知识水平不高、安全意识不强、燃具产品和服务质量良莠不齐等。并以事故预防控制理论为指导,提出广州市天然气应用预防与安全管理应采取的技术、教育、强化等3方面对策。     

煤矿危险源风险预警与控制的研究

根据现代安全管理的理论与方法,结合煤矿人-机-环境特点和不同煤矿事故的发生机理,对煤矿危险源风险预警和控制的基本理论和方法进行了探讨,提出了基于危险源的煤矿风险预警与控制的一般流程,给出煤矿危险源辨识、风险评价、监控和预警的方法,为煤矿安全管理信息系统提供理论基础。     

周年磷肥旱季集中底施对玉-稻轮作磷肥效应的影响

春玉米-晚稻水旱轮作是近年来南方稻区种植制度变化下出现的新型两熟制模式。明确两季作物间磷肥的合理分配对玉-稻轮作作物产量与磷素利用效率的影响,对玉-稻轮作养分高效与高产协同实现,及丰富对水旱轮作前后季作物养分利用关系的认识具有理论意义。采用春玉米-水稻周年轮作田间试验,根据晚稻季磷肥前移至玉米季做底肥施用的比例及周年施磷量,设置7个磷肥施用处理,分别为两季作物均不施磷(P_0)、两季作物均按常规方法施磷(P_1)、1/3晚稻季磷肥前移(P_2)、2/3晚稻季磷肥前移(P_3)、全部晚稻季磷肥前移(P_4)、全部晚稻季磷肥前移且周年总施磷量减少15%(P_5)、全部晚稻季磷肥前移且周年总施磷量减少30%(P_6),分析了不同施磷处理作物产量、磷素吸收量及磷素利用效率的变化。与P_1相比,P_3与P_4处理显著提高了晚稻花后干物质的分配比例及晚稻产量,且其周年产量分别提高了4.87%和6.74%;P_5处理晚稻产量与P_1处理差异不显著,但P_6显著降低了晚稻产量。晚稻季磷肥前移施用明显促进了玉米及晚稻对磷素的吸收,显著降低了磷素的表观盈余量。与P_1处理相比,P_2、P_3、P_4处理两季作物周年土壤磷素依存率分别减少了11.63%、26.47%与22.08%。从磷肥利用效率看,P_4处理的磷肥周年累积回收效率、农学利用效率、偏生产力及磷肥产量贡献率均显著高于P_1处理,分别提高了102.46%、194.83%、6.73%与176.16%。与P_1处理相比,P_5处理周年磷肥产量贡献率及农学利用效率差异不显著,但分别提高了其磷肥回收效率与偏生产力32.56%和58.05%。玉米季施用的磷肥对晚稻有明显的后效作用,且比晚稻季施用磷肥具有更高的磷肥利用效率。所以在春玉米免耕复种晚稻时,可将晚稻季的磷肥全部前移至玉米季施用,并可减少15%周年施磷量。     

基于布谷鸟搜索优化的光伏电站辐照强度预测

针对光伏电站日前小时短期辐照强度的预测准确性问题,且考虑到支持向量机的学习参数对预测模型的性能有较大影响,为进一步提高数据的预测精度,利用布谷鸟搜索算法对支持向量机的惩罚因子c和核参数g进行优化,提出了一种基于布谷鸟搜索算法和支持向量回归的组合预测方法。仿真结果表明:该方法大大提高了光伏辐照强度预测的准确性和精度,可行且高效,适用于光伏在线预测。     

珠江三角洲4种淡水养殖鱼类重金属的残留及食用风险评价

为全面了解珠江三角洲淡水水产品中重金属污染现状,评估其生态风险与食用安全,于2014年8月至2015年8月采集罗非鱼、草鱼、乌鳢及鳜鱼主要养殖鱼类样品共计57份,采用原子荧光光谱仪(AFS),电感耦合等离子体质谱(ICP-MS)仪进行分析测定,并采用单因子污染指数(Pi)、重金属污染指数(MPI)、每周可耐受摄入量(PTWI)以及食入健康风险指标(Ri总)分别评估其污染程度、食用安全性与健康风险。结果表明,样品中Cr、Ni、Cu、Zn、As、Cd、Hg、Pb的含量范围分别为0.020~3.240,0.020~0.800,0.110~1.100,0.190~19.970,0.030~1.480,nd~0.606,0.003~0.118,0.040~0.803 mg·kg-1(湿重),Cr、As、Cd、Pb在水产品中超标率大小依次为As(7.0%),Pb(7.0%),Cd(5.3%),Cr(1.8%)。Pi结果表明,目前珠江三角洲养殖水域水产品中Cu与Zn残留处于正常范围内,Cr和Hg有少量样品为轻度污染,Pb、Cd与As存在重度污染样品,所占比例为2.86%、6.02%和5.74%。MPI结果显示不同水产品污染程度为乌鳢>鳜鱼>罗非鱼>草鱼,总体上各种水产品MPI依然处于较低的水平;食用安全性结果显示,目前成人每周摄入水产品是安全的,但乌鳢Cr,罗非鱼As含量较高分别达到PTWI的37.76%和19.51%,表明水产品中Cr、As残留可能存在一定的食用安全隐患。健康风险模型结果显示,所有样品均未超过国际辐射防护委员会(ICRP)的推荐的最大可接受水平(5×10-6a-1)。综合分析珠江三角洲淡水养殖主要水产品可知,其尚未出现明显的污染安全问题,但As与Cr等元素的潜在风险值得进一步关注。